Treatment of lubricating oils



Patented Nov. 24, 1942 TREATMENT OF LUBRICATING OILS Sidney Masher, New York, N. Y., asslgnor to Musher Foundation Incorporated, New York, N. Y., a corporation of New York No Drawing. Application April 23, 1940, Serial No. 331,186

19 Claims.

low, it being understood, however, that this more detailed description is given by way of illustration and explanation only, and not by way of limitation, since various changes therein may be made by those skilled in the art without departing from the scope and spirit of the present invention. 7

It has been found that. there are present in molasses, particularly blackstrap molasses, desirable products which may be utilized as inhibitors to corrosion of lubricating oils and which show potent corrosion inhibiting eifects.

The molasses particularly used in accordance with the present invention is known as blackstrap molasses and is obtained preferably from the sugar cane refining industry. There may also be utilized blackstrap molasses obtained from the sugar beet industry, as well as sorghum molasses.

The molasses utilized to inhibit lubricating oil corrosion is the non-crystallizable fraction of the water soluble extract of the sugar cane or beet left after the crystallization of substantially all of the sucrose crystals in the refining i cane sugar or beet sugar.

Where a small amount of blackstrap molasses is added directly to the lubricating oil and the lubricating oil then heated to a temperature of at least about 300 F. and desirably to a temperature between 400 F. 'and 600 F., a definite anti-corrosive efiect is obtained. I

It has also been found possible for the blackstrap molasses to be thoroughly admixed with lubricating oil in a small amount, such as in an amount of less than 10%, preferably at a slightly elevated temperature, such as between 200 F. and 300 F., and then the charred or undissolved blackstrap molasses may be filtered or removed from the lubricating oil. The lubricating oil will thereupon have a much superior keeping quality and will have a lessened tendency toward the formation of corrosive substances when in ccntact with metallic surfaces.

There may be used in accordance with the present invention less than about 10% of blackstrap molasses on its solids weight basis against the weight of the lubricating oil and frequently as little as about 2% to 5% shows desirable results.

Where the blackstrap molasses is added directly to the lubricating oil, it is diflicult to obtain the full benefits of the blackstrap molasses because the blackstrap molasses contains constituents which are insoluble in the lubricating oil.

Under these circumstances, the blackstrap molasses may be reduced substantially to dryness as by heating under reduced or atmospheric pressure, preferably in an acidified medium. The blackstrap molasses in substantially dehydrated and moisture-free form may thereupon be combined with the lubricating oil in order to exert the desired antioxygenic effect, followed by filtration of the insoluble portion of the molosses.

In another way of carrying out the present invention, the blackstrap molasses may be dried and the dried blackstrap molasses added to the lubricating oil in an amount of less than about 10% and then filtered to remove the undissolved blackstrap molasses residues.

It has been found desirable for the blackstra molasses to be added to the lubricating oil at a temperature of at least about 200 F. to 400 F. at which the sugars of the blackstrap molasses become charred and for the undissolved portion of the blackstrap molasses to be then removed from the lubricating oil by filtration, centrifuging or similar means leaving behind a substantially stabilized lubricating oil and particularly stable to corrosion and oxidative influences.

Another procedure for carrying out the present invention is for the blackstrap molasses containing at least about 50% to total solids to be combined with or emulsified with from 1 to 5 parts by weight of the lubricating oil and for the combination then to be subjected to a temperature sufliciently high to drive oil all the moisture, such as between 210 F. and 350 F. This combination, with or without filtration to remove the insoluble portion, may then be utilized for addition to the lubricating oil in the desired amount and preferably at the elevated temperature, followed by filtration of the insoluble por tion of the blackstrap molasses.

As another means for carrying out the present invention, the blackstrap molasses. desirably in dehydrated condition, may be subjected to extraction to remove the potent antioxygenic substances from the blackstrap molasses.

' polyphenols,

It is, of course,.possib1e to use derivatives of the above identified compounds in which one or more of the hydrogen atoms in the benzene or naphthalene nucleus or in the aliphatic side chain or in the amino or hydroxy groups, is or are replaced by alkyl, aryl, hydroxy, amino,

' alkoxy or nitro groups although this is usually extract that is obtained may then be added to the lubricating oil in a minor amount.

Where the solvent is miscible with and not objectionable for use in the lubricating oil, it' may be added directly thereto while containing combination consisting of 10 parts of blackstrap molasses with from 1 to 20 parts, and desirably about 10 parts, of lecithin as obtained from soya bean, cottonseed or corn oil, and this combination may then be directly added to the lubricating oil or dehydrated and subjected to extraction in the manner indicated above. Or the blackstrap molasses may first be dehydrated and extracted and the extract then combined with lecithin and used for addition to the lubricating oil in accordance with the present invention.

The blackstrap molasses and the extracts thereof, as described above, may very desirably, preferably with the addition of a phosphatide, be combined with other compounds including particularly the aryl phosphites, such as triphenyl phosphite, and other hydroxy and/or amino aromatic compounds.

For example, the blackstrap molasses or its extracts, with or without lecithin and similar phosphatides, may be combined with certain aromatic hydroxy compounds and amino compounds and particularly polyhydroxy, polyamino and aminohydroxy compounds which are most effective and surprisingly active in combination in stabilizing lubricating oils.

Although it is preferred to use the polyhydroxy, polyamino, and hydroxyamino nuclear compounds, it also has been found satisfactory to use even poly-nuclear monohydroxy or monoamino compounds. I 7

Among the preferred compounds that may be employed in combination with blackstrap molasses with or without lecithin for addition to the lubricating oil are hydroquinone, pyrogallol, catechol, eugenol, thymol, tannins, tannic acid, alphanaphthol, napthoquinones, phenylbetanaphthylamine, and para-aminophen01,- monobenzyl-p-aminophenol, and other aminophenols, diphenylethylenediamine, benzyl-mphenylenediamine, and other aromatic diamines, p-aminodimethylaniline and diphenylhydrazine. These various materials are included in the expression substituted aranes.

Less preferably, aromatic acids may be utilized, particularly aromatic carboxy acids containing one or' more amino groups or hydroxy groups either inthe nucleus or in aliphatic side chains.

not preferred.

The blackstrap molasses or its extracts may be employed in any proportion in combination with the phosphatides or other organic compounds including, for example, the phosphite esters and substituted aranes referred to herein, but it is preferable to use at least about 40% to 60% of the blackstrap molasses composition with 60% to 40% of the added phosphatide and/or phosphite ester or polyhydroxy arane.

It is of particular importance to utilize in accordance with the present invention combinations of blackstrap molasses or its extracts with or without lecithin and the alkyl or aryl phosphites which appear to co-react with the blackstrap molasses or its extracts and with or 'without lecithin in order to produce a highly desirable anti-corrosive eflect. Among the different types of phosphites that may be employed in combination with blackstrap molasses and with or without lecithin and particularly when subjected to elevated temperatures are tri-phenyl, tri-cresyl, tri-xylyl, tri-naphthyl, tri-anthracyl, tri-propyl, tri-butyl, tri-amyl and/or tri-hexyl phosphites and various mixed aryl-alkyl phosphites or even alkaryl phosphites or aralkyl phosphites.

Sometimes it has been found possible to use monoor di-esters instead of the tri-esters, but these are generally not as effective as the triesters.

It is also possible to combine with the blackstrap molasses or its extracts and with or without lecithin, but in amounts which should be less than about 50% of the total combination, other amino or nitrogen containing aromatic, aliphatic or heterocyclic compounds having from '2 to 30 or more carbon atoms, 1 or more nuclear or poly-nuclear groups, and 1 to 3 alkyl, aryl,

alkaryl or aralkyl substituted or unsubstituted amino, hydroxy or carboxy groups. Among the compounds that may be employed in combination with blackstrap molasses are phenylhydrazine, cyclohexylamine, triethanolamine and hexamethylenetetramine.

Briefly, the compounds that may be combined with a molasses for treatment of mineral lubricating oils are:

(a) Monohydroxy-aryl compounds such as pcresol, substituted 0- and p-phenols, and betanaphthol and their derivatives;

(2)) Monoamino-aryl-compounds such as aniline, substituted 0-* and -p-alpha and betanaphthylamines, methyl and ethylalphanaphthylamines, diphenylamine, phenylalphanaphthylamine, aldoalphanaphthylamine, m-toluidine, phenylbetanaphthylamine, acetalanaline, aromatic amines, dimethylaniline, amino-diphenyls, .benzidine and amino-naphthols and their derivatives;

(c) Amine condensation products with aldehydes and ketones, such as benzalaniline, formylalphanaphthylamine, aldehyde-amine and ketone-amine condensation products, butyraldehyde-aniline and, aldol-aniline and their derivatives;

(d) Nitrogen ring compounds, such as diphenylguanidine, p-dimethylamino-phenyl-p-phenetidyl-guane, pyridine, acridine, tx'lazine, pi-

rivatives;

peridine, quinoline and morpholine and their derivatives;

iasses at an elevated temperature in excess of '(e) Sulfur compounds, such as thiodiphenyldisul- (h) Aliphatic oxygen compounds, such as octadecyl alcohol and trioxymethylene and their derivatives.

Although lecithin is preferred for use with molasses in accordance with this invention, it is possible to use cephalin and other similar phosphatides of plant or animal origin.

It is also possible to utilize in combination with molasses or its extractsvarious organic sulfur compounds, such as the thiophenols, thioamines, mercaptans, and sulfides such as for example, thiodiphenylamine or phenyl disulfide.

The stabilizing procedures of the present invention are most applicable to non-volatile high molecular weight aliphatic hydrocarbons, and these procedures may also be utilized with high boiling liquid hydrocarbon mixtures derived from other sources than petroleum and even in some instances they may be used with solid high molecular weight hydrocarbon mixtures.

Less preferably, these stabilizing procedures may be employed with non-aliphatic hydrocar bons of high boiling point and still less preferably with high molecular weight glyceride oils, particularly the triglycerides of high molecular weight fatty acids having 12 to 36 carbon atoms, which acids may contain if desired one or more double bonds or hydroxy groups.

The invention is less preferably applicable to hydrocarbon compounds of volatile nature or having a boiling point less than about 200 F. to

250 F. or to rubbery orgummy hydrocarbon mix- 3. A process of improving lubricating oils to decrease sludge formation and also to decrease their tendency to cause corrosion of metal surfaces, which comprises treating such oil with a relatively small amount of a dehydrated molasses at an elevated temperature.

4. A process of improving lubricating oils to decrease sludge formation and also to decrease their tendency in cause corrosion of metal surfaces, which comprises treating such oil with a relatively small amountof an organic solvent extract of a molasses at an elevated temperature.

5. A process of improving lubricating oils to decrease sludge formation and also to decrease 6. A process of improving lubricating oils to decrease sludgeformation and also to decrease their tendency to cause corrosion of metal surfaces, which comprises treating such oil with a relatively small amount, less than 10%, of a combination of about equal proportions of lecithin and molasses at an elevated temperature of between 400" F. and 600 F. L

'1. A process of improving lubricating oils to decrease sludge formation and also to decrease their tendency to cause corrosion of metal surfaces, which comprises treating such oil with a relatively small amount of a combination of a molasses and a phosphite ester at an elevated V temperature.

8. A process of improving lubricating oils to decrease sludge formation and also to decrease their tendency to cause corrosion of metal surfaces, which comprises treating such oil with a relatively small amount of a combination of an organic solvent extract of a molasses and a phosphite ester at an elevated temperature. 9. A process of improving lubricating oils to decrease sludge formation and also to decrease their-tendency to cause corrosion of metal surfaces, which comprises treating such oil with a relatively small amount of a combination of a molwses and an organic compound selected from the group consisting of the phosphatides, phosphite esters and polyhydroxy aranes at an elevated temperature.

10. A process of improving lubricating oils to decrease sludge formation and also to decrease their tendency to cause corrosion of metal surfaces, which comprises treating such oil with a relatively small amount of a combination of an organic solvent extract of a molasses and an organic compound selected from the group consisting of the phosphatides, phosphite esters and polyhydroxy aranes at an elevated temperature.

11. A process of treating hydrocarbon lubrieating oils to render them less subject to the development of corrosive substances which comprises adding to such oils a small quantity of a dehydrated blackstrap molasses and then-heating the oil containing the molasses to a temtheir tendency to cause corrosion of metal surperature in excess of 200 F. to 300 F. to char the same.

12. A process of improving lubricating oils which comprises heating such oils with a relatively small amount of molasses, whereby said lubricating oils are rendered less subject to corrosion and sludge formation.

13. A process of improving lubricating oils which comprises heating such oils with a relatively small amount of a dehydrated molasses, whereby said lubricating oils are rendered less subject to corrosion and sludge formation.

14. A process of improving lubricating oils which comprises heating such oils with a relatively'small amount of an organic solvent extract of blackstrap molasses, whereby said lubrieating oils are rendered less subject to corrosion and sludge formation.

15. A lubricating oil having decreased tendencr towards sludge formation and decreased tendency towards causing corrosion of metal surfaces, said lubrlcating oil having been combined at an elevated temperature with a small amount of the dehydrated constituents of molasses.

16. A lubricating oil having decreased tendency towards sludge formation and decreased faces, said lubricating oil having been combined at an elevated temperature with a small amount of the dehydrated constituents of molasses and a small amount of a phosphatide.

17. A lubricating oil having decreased tend 5 ency towards sludge formation and decreased tendency towards causing corrosion of metal surfaces, said lubricating oil having been combined at an elevated temperature with'a small amount of the organic solvent extracted, blackstrap mo-' 10 lasses solids.

18. A lubricating oil having decreased tend-' ency towards sludge formation and decreased tendency towards causing corrosion of metal surfaces, said lubricating oil having been combined .15

ency towards sludge formation and decreased tendency towards causing corrosion 01' metal surfaces, said lubricating oil having been combined at an elevated temperature with a small amount of the dehydrated constituents of molasses, said combination being caused to take place at an elevated temperature in excess of between 400 F. and 600 F. I

' SIDNEY MUSHER. 

